Adsorption Isotherm and Kinetics of Dibenzofuran on Granular Activated Carbons

The adsorption of dibenzofuran on three commercial granular activated carbons (ACs) was investigated by dynamic experiment to correlate the adsorption equilibrium and kinetics with the structure of activated carbons.Physical properties including surface area, average pore diameter, micropore area and micropore volume of the activated carbons were characterized by N2 adsorption experiment on ASAP2010. To calculate the adsorption parameters, adsorption isotherm data were fitted to the Langmuir equation, and adsorption kinetic data were fitted to the linear driving force (LDF) diffusion model. From the correlation results, it is concluded that the adsorption equilibrium and diffusion coefficient of dibenzofuran on activated carbon are controlled respectively by the total adsorbent surface area and the adsorbent pore diameter.

Polychlorinated dibenzo-p-dioxins and dibenzofurans in flue gas emissions from municipal solid waste incinerators in China

Polychlorinated dibenzo-p-dioxins and furans （PCDD/Fs） emissions in flue gas from two types of municipal solid waste incinerators （MSWIs） most commonly used in China were investigated in this study. The selected incinerators include two grate-type MSWIs： MSWI-A （350 t/d） and MSWI-B 050 t/d）, and two fluidized bed MSWIs： MSWI-C （400 t/d） and MSWI-D （400 t/d）, which are all equipped with semi-dry lime scrubber and bag filter except MSWI-D equipped with cyclone and wet scrubber （WS） as air pollutant control device （APCD）. Results indicated that the emission concentration and the international toxic equivalents （I-TEQs） of the PCDD/Fs from the stacks were in the range of 1.210-10.273 ng/Nm^3 and 0.019-0.201 ng I-TEQ/Nm^3, respectively. They were greatly lower than the emission regulation standard of PCDD/Fs in China （1.0 ng I-TEQ/Nm^3）. However, only the PCDD/Fs emission level from MSWI-C was below 0.1 ng I-TEQ/Nm^3. Although the homologue profiles were distinct, the contributions of the 2,3,7,8-subsituted congeners to the total I-TEQ were similar among all the investigated MSWIs. Two major 2,3,7,8-substituted congeners, 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD, account for 47% and 9% （average values） of the total I-TEQ values, respectively. The correlation between PCDD/Fs levels and composition of flue gas was also discussed.

Two New Dibenzofurans from the Underground Parts of Ligularia intermedia

Two new dibenzofurans, 7,8-dimethoxy-4-methyldibenzofuran-1-carboxaldehyde, named ligumedial (1) and 7,8-dimethoxy-4-methyldibenzofuran-1-carboxylic acid, named ligumediaoic acid (2), have been isolated from the underground parts of Ligularia intermedia. Their structures were elucidated by spectroscopic methods.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in surface sediment and bivalve from the Changjiang Estuary, China

Surface sediments and bivalves were collected from the Changjiang Estuary in December 2003 and November 2004, respectively. Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in these samples were measured with high-resolution chromatography (HRGC)/High Resolution Mass Spectrometer (HRMS). The concentrations of total PCDD/Fs and toxic equivalent (TEQ) were 169.83±119.63 and 0.81±0.36 pg/g dry weight (dw) in sediments, and 580.33±240.17 and 7.24±3.65 pg/g dw in bivalves. The homolog compositions of PCDD/Fs were similar among samples, the most abundant congener was octa-chlorinated dibenzo-p-dioxin (OCDD) and then octa-chlorinated dibenzofuran (OCDF) and 1,2,3,4,6,7,8-hepta-chlorinated dibenzo-p-dioxin (HpCDD). The herbicide pentachlorophenol (PCP) and sodium pentachlorophenol (Na-PCP) were proved the main source of PCDD/Fs in this area.

Distribution and geochemical significance of dibenzofurans,phenyldibenzofurans and benzo[b]naphthofurans in source rock extracts from Niger Delta basin,Nigeria

The distribution and geochemical significance of dibenzofurans,phenyldibenzofurans and benzo[b]naptho-furans in source rocks from Niger Delta basin,Nigeria,were investigated by Rock-Eval pyrolysis and gas chro-matography--mass spectrometry(GC--MS).The data obtained from the source rocks evaluation showed that the rock samples contained type 1/III kerogen capable of generating oil and gas and were within immature to early mature stage.The relative abundance of the Cor,C1-and C2-dibenzofurans range from 1.75%to 29.82%,27.60%to 40.52%and 29.66%to 6889%,respectively.The diben-zofurans were dominated by C-dibenzofurans.Among the C1-dibenzofurans,2-+3-methyldibenzofuran was the most abundant in the rock samples while 1-methy ldibenzofuran appeared to be the least.The relative abundance of benzo[b]naphtho[1,2-d]furan(1,2]BNF),benzo[b]naph-tha[2,1-d]furan(2.1]BNF)and benzo[b]naphtha[2,3-d]fu-ran([2.3]BNF)in the rock extracts range from 12.01%to 52.58%,32.61%to 75.219%and 10.27%to 52.43%.The wide range of values recorded for the three isomers of benzo[b lnapthofurans in the samples suggest source rocks formed from mixed organic matter.Among the pheny ldibenzofuran isomers,4-pheny ldibenzofuran was the most abundant while 1-phenyldibenzofuran was the least.Phenyldibenzofuran ratio-1(PhFR-1)and pheny ldibenzofuran ratio-2(PhFR-2)values range from 0.13 to 1.20 and 0.11 to 2.11,respectively.The resuls showed that the relative abundance of PhFR-1 and PhFR-2 increase gradually with increasing burial depth and maturity(VRo≤0.77%,MPI-1≤0.62.Tmax s 443℃),and have a good correlations with calculated vitrinite reflectance.MPI-I and maximum Temperature(Tmax)-This range of values suggested immature to early mature source rocks.The source rocks were found to have shale and coul lithologics and deposited in a lacustrine/fuvial deltaic settings within immature to early mature stages based on the distribution of dibenzofurans,pheny ldiben-zofurans and benzo[b]naphthofurans in the source rocks.This study showed that dibenzof urans,phenyldibenzofu-rans and benzo[b]naphthofurans were ffcive in deter-mining the origin,depositional environment and thermal maturity of source rocks in Niger Delta basin,Nigeria.

ACTIVATION ENERGY OF DESORPTION OF DIBENZOFURAN ON ACTIVATED CARBONS

Three kinds of commercial activated carbons, such as Norit RB1, Monolith and Chemviron activated carbons, were used as adsorbents for adsorption of dibenzofuran. The average pore size and specific surface area of these activated carbons were measured. Temperature Programmed Desorption (TPD) experiments were conducted to measure the TPD curves of dibenzofuran on the activated carbons, and then the activation energy for desorption of dibenzofuran on the activated carbons was estimated. The results showed that the Chemviron and the Norit RB1 activated carbon maintained higher specific surface area and larger micropore pore volume in comparison with the Monolith activated carbon, and the activation energy for the desorption of dibenzofuran on these two activated carbons was higher than that on the Monolith activated carbon. The smaller the pore of the activated carbon was, the higher the activated energy of dibenzofuran desorption was.

Surface Electrostatic Potentials of Polychlorinated Dibenzofurans and Their Applications in Quantitative Structure-toxicity Relationships

Polychlorinated dibenzofurans (PCDFs) represent an important kind of serious pollutant. They are highly toxic and persistent in environment. In this paper, geometrical optimizations and subsequent calculations of electrostatic potentials (ESPs) on molecular surface have been performed for all 135 PCDF congeners at the HF/6-31G* level. The effects of substitution value and variation of substitution position upon the surface ESPs have been discussed. A series of statistic-based structural descriptors derived from the surface ESPs have been calculated. For some PCDF congeners, linear relationships between aryl hydrocarbon receptor (AhR) biding affinity and aryl hydrocarbon hydroxylase (AHH) induction potency as well as theoretical descriptors have been established by multiple linear regression method. It appears that the quantities derived from the surface ESPs, Vs,min, Vs , VS +, σ+ and Nvmin, 2 together with the molecular surface area and the energy gap between HOMO and LUMO can be well used to express the quantitative structure-toxicity relationships of PCDFs.

Study on the Intramolecular Hydrogen Bonds of Dibenzofurans, Xanthones and Anthraquinones with One or Two Positions Substituted by Hydroxyls

The thermodynamic properties of dibenzofurans （DFs）, xanthones （XTs） and an-thraquinones （AQs） with one and two positions substituted with hydroxyls in the ideal gas state at 298.15 K and 1.013×10^5 pa were calculated at the B3LYP/6-311G^＊ level using Gaussian 03 program. The isodesmic reactions were designed to calculate the standard free energy of formation （△fG^θ）. Three types of hydrogen bonds exist in the three kinds of chemicals and their bond energies were ascertained as 7-15, 15-23 and 49-58 kJ·mo1^-1 respectively by comparing the △fG^θ values. Electronic density topology analysis was applied to validate the strength of bond.

Determination of the Most Toxic Polychlorodibenzofurans in Fresh Milk from Southwest Iran

Background: Today’s presence of polychlorinated dibenzofurans (PCDFs) in foodstuff, such as milk and milk products, is considered to be the major concern for human health. This study was aimed to determine the concentrations of the most toxic congeners of furans in pasteurized milk samples produced in southwest Iran. Material and method: 15 composite samples of pasteurized milk were collected from 3 major dairy factories in Khuzestan Province (southwest of Iran) in summer, autumn and winter from July 2011 to March 2012. After precipitation of the proteins, fat phase was reduced and extracted with hexane and ether. After dehydration, furans existed in fat percolated with hexane through a column chromatography that contained respectively silica gel/silver nitrate, silica gel, silica gel/sulphuric acid and with percolating output through another column that contained activated charcoal and silica gel and washed the lower column with a mixture of dichloromethane-hexane and toluene, concentrated and dissolved in mobile phase and analyzed using HPLC: 150 mm × 4.6 mm ID, 5 μm cosmosil 5 NPE column equipped with a UV detector at 254 and 235 nm, mobile phase: methanol/water (80:20, v/v) at flow rate of 1 ml/min. Results: All samples were found to be contaminated with furans. The average concentration of 2,3,7,8 TCDF and 2,3,4,7,8 PCDF were 1.91 pg/g and 1.77 pg/g in lipid content ranging from 2% to 3% respectively. The mean total content of furans in milk fat was 0.36 TEQ (Toxic Equivalency) pg/g which was below the recommended EU (European Union) threshold value 3 pg (WHO-PCDFs-TEQ/g fat). Also, result showed that there were statistically significant differences between each factory during 3 seasons.

Pure Rotational Spectrum of Dibenzofuran in Range of 2-6 GHz

We report the observation and assignment of the rotational spectra of dibenzofuran measured in the range of 2-6 GHz with a newly constructed broadband chirped-pulse Fourier transform microwave(cp-FTMW)spectrometer.An analysis of the microwave spectra led to the assignment of 40 b-type transitions,resulting in the accurate determination of the rotational constants A=2278.19770(38)MHz,B=601.12248(10)MHz,and C=475.753120(98)MHz.

2-Nitrobenzofuran as Dienophile in Polar Diels-Alder Reaction： A Simple Dibenzofurans Synthesis

2-nitrobenzofuran is studied as dienophile in polar thermal Diels-Alder reactions with normal electron demand using several structurally different dienes. A very strong electron-acceptor group, such as nitro group, enhances the dienophilic character of these heterocyclic compounds and owing to the fact that this substituent is easily extruded under thermal conditions this reaction sequence becomes a simple method of organic compound＇s families with heteroatom rings preparation. Part of this work is specifically concerned with theoretical studies. The global and local electrophilicity and nucleophilicity indexes were calculated for the dienophile and dienes used in this work. A concise synthesis of dibenzofurans has been development via cycloaddition reactions.

Polychlorinated Dibenzofurans and Dibenzo-p-Dioxin in Tree Bark from an Industrialized Area: What the 2,3,7,8-Cl Substituted Congeners Tell Us, and What Is Missing

We analyzed polychlorinated dibenzofurans (PCDF) and dibenzo-p-dioxins (PCDD) in 27 tree bark samples from the industrialized area near Sauget, Illinois, USA. The trees were located within 4 km of the W. G. Krummrich (WGK) plant, the oldest and largest chemical plant in Sauget, with 24 of 27 samples collected from residential areas. The percent of total PCDF or PCDD profiles of ten 2,3,7,8- Cl substituted PCDF and seven PCDD congeners is homogeneous: 90% of the variance among the samples is explained by 3 eigenvalues in a principal components analysis. The homogeneity of the data suggests that samples were affected by similar types of sources which may have been influenced by electric power generation, chemical waste incineration, and large-scale thermal production of chlorinated chemicals. Quantitatively, the 2,3,7,8-Cl substituted congener analysis does not account for 90% of the concentration of tetra- and penta-Cl homologues and 80% of hexa-Cl and 50% of hepta-Cl homologues. The World Health Organization stated during establishment of toxic equivalence factors (TEF, 2005 version) that calculation of toxic equivalents (TEQs) is not suitable for abiotic matrices, such as tree bark, which are not involved in human exposures. Our results show that the non-2,3,7,8-Cl substituted congeners have high concentrations and should be included in analysis.

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

Ten series of aromatic hydrocarbon compounds (biphenyl, naphthalene, phenanthrene, anthracene, retene, chrysene, benzoanthracene, dibenzofuran, fluorene, dibenzothiophene) isolated from seven Triassic and Jurassic lacustrine mudstone samples and three swamp coal samples, as well as five crude oil samples collected in the Kuche depression of the Tarim Basin, NW China, have been analysed by GC-MS techniques. It is found that the relative abundances of dibenzofuran series are higher in the three swamp coal samples than those in the lacustrine mudstone samples. Based on the similar relative abundances of dibenzofuran series, especially dibenzofuran compound, in the TICs of aromatic hydrocarbons, crude oils from wells SA3 (K), YTK5 (E, K) and QL1 (E) are thought to have been derived predominantly from the coals of the Lower Jurassic Yangxia Formation or Middle Jurassic Kezilenuer Formation, whereas those from wells YM7 (O) and YH1 (E) were derived mainly from Triassic and Jurassic lacustrine mudstones in the Kuche depression. This is the first report about how to distinguish coal-generated oils from lacustrine mudstone-generated oils in the Kuche depression in terms of the dibenzofuran series. The present paper has enlightening and directive significance for further oil-source rock correlations and oil and/or gas exploration in the Kuche depression of the Tarim Basin.

EXAMINATION OF POLYCHLORINATED DIBENZO-P-DIOXINS AND POLYCHLORINATED DIBENZOFURANS INTO PROCESS WATER OF KRAFT PULP BLEACHING MILL FROM ASPECT OF ENVIRONMENTAL WATER QUALITY

Process water of a pulp mill with kraft cooking, oxygen delignification and chlorine bleaching or chlorine dioxide (ECF) bleaching was examined from an aspect of a new level for environmental water quality in Japan. According to the new level, a concentration of dioxins consisting of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (PCBs) in environmental water is restricted to less than 1 pg- TEQ/L. We clarified that the 2,3,7,8-tetrachlorodibenzofuran (TCDF) concentrations were 0.5 pg/L or less. In addition, a main source of 1,3,6,8- and 1,3,7,9-tetrachlorodibenzo-p-dioxins in the process water seemed to be an agrochemical in water supplied from a river.

Polychlorinated dibenzo-p-dioxins and dibenzofurans in different tissues of the cormorants (Phalacrocorax carbo) from Dongting Lake,China

Tissue distribution provides important information regarding the pharmacokinetic behavior of pollutants and is invaluable when analyzing the risk posed to avian species by the exposure to such kind of pollutants. In this study, concentrations of polychlorinated dibenzo-p-dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） were determined in muscle, liver, spleen, kidney, stomach, gall bladder, skin, heart, pancreas, intestine and lung tissue extracts of cormorants collected from Dongting Lake, China. Tissue distribution results showed preferential accumulation of PCDD/Fs in both liver and skin. The total concentration of PCDD/Fs ranged from 421 to 5696 pg/g lipid weight. Octachlorinated dibenzo-p-dioxin （OCDD） was the predominant congener in all tissues and contributed between 31% and 82% to all 17 PCDD/Fs in different tissues. The liver/muscle ratios progressively increased with the degree of chlorination of PCDDs, except for OCDD. The relative toxic potential of PCDDs and PCDFs in tissues were calculated using the World Health Organization （WHO） Toxic Equivalency Factors （TEFs） for birds. The concentrations of WHO-toxic equivalent in different tissues ranged between 14.8 and 2021 pg/g lipid weight. These results indicated PCDD/Fs may have been bio-accumulated in cormorant via food-web. Furthermore, when compared with studies reported in the literatures, the PCDD/Fs levels in the cormorant collected from Dongting Lake were still relatively high.

某生活垃圾焚烧厂排放废气、飞灰、环境空气和土壤中各二噁英类单体分布特征

以某生活垃圾焚烧企业为研究对象,研究其烟道气废气、焚烧飞灰、企业周边环境空气和土壤中二噁英的水平和各二噁英类单体指纹分布特征,研究结果表明,废气中的二噁英呈现出冬季稍高于夏季的排放特征,呋喃对总∑TEQ的贡献率范围为72%-90%.飞灰作为垃圾焚烧中二噁英的主要捕集途径,TEQ浓度季度变化比废气更加明显,呋喃对总∑TEQ的贡献率范围为74%-81%.环境空气和土壤中二噁英的季度分布特征与废气、飞灰的分布特征一致,且主导风向土壤中二噁英的TEQ浓度明显高于次主导风向.环境空气单体指标中呋喃对总∑TEQ的贡献率与废气和飞灰规律一致,说明该区域环境空气中的二噁英与企业排放废气中的二噁英具有同源性.与废气、飞灰和环境空气相比,土壤中呋喃与二噁英的比值和呋喃对总∑TEQ的贡献率存在差异,说明土壤中的二噁英并非单一来源于企业排放废气.废气、飞灰、企业周边环境空气和土壤中的17种PCDD/Fs单体中含量最丰富的是O8CDD,PCDDs的浓度随着取代氯原子个数的增加而增大.17种PCDD/Fs单体中对毒性当量贡献最大的单体是2,3,4,7,8-P5CDF.2,3,7,8-T4CDD是引起废气中二噁英排放呈现出冬季稍高于夏季的特征污染因子,需要重点关注.

Supported Pt-Ni bimetallic nanoparticles catalyzed hydrodeoxygenation of dibenzofuran with high selectivity to bicyclohexane

Catalytic hydrodeoxygenation(HDO)is one of the most effective methods to upgrade the oxygen-containing compounds derived from coal tar to valuable hydrocarbons.Herein,an efficient bimetallic catalyst Pt_(1)Ni_(4)/MgO was prepared and applied in the HDO of dibenzofuran(DBF).High yield(95%)of the desired product bicyclohexane(BCH)was achieved at 240℃and 1.2 MPa of H_(2).Superior catalytic performance could be ascribed to the"relay catalysis"of Pt sites and Ni sites,and the reaction pathway is proposed as well.Scale-up experiment and recyclability test were also performed,which demonstrated the recyclability and promising potential application of Pt_(1)Ni_(4)/MgO.

金属载体强相互作用对二苯并呋喃加氢脱氧反应影响

煤焦油作为煤炭热解的主要产品之一,产量大、用途广,合理有效地利用中低温煤焦油可促进煤炭资源的清洁高效转化。通过催化加氢脱氧实现对中低温煤焦油中氧原子脱除,可提高油品的氢碳比和稳定性,获得高品质燃料。二苯并呋喃含量高,反应活性低,选择其作为模型化合物,用于加氢脱氧反应研究。金属载体强作用(SMSI)的调控被广泛用于多相催化领域,但其对加氢脱氧反应影响尚不清楚。为探究SMSI对加氢脱氧反应的作用机理,用镍钛锆水滑石作为催化剂前驱体,通过改变Zr的比例,制备不同金属载体强相互作用的Ni基催化剂(Ni/mZrO_(2)@TiO_(2-x),m=0~0.5),用于模型化合物二苯并呋喃的加氢脱氧反应。通过HRTEM、H_(2)-TPD和CO-pulse等表征发现催化剂在还原中部分载体被还原为TiO_(2-x)并在Ni颗粒表面形成包覆层,产生氧空位。随着Zr比例增大,SMSI强度降低,导致包覆层和氧空位含量减少。280℃、6 MPa下对不同SMSI强度的催化剂进行活性评价,发现随着SMSI强度降低(Zr比例增大),脱氧产物收率由60.7%增至94.8%后降至66.9%,在Ni/0.4ZrO_(2)@TiO_(2-x)催化剂上呈现最佳脱氧性能;且该催化剂经5次循环活性未出现明显下降,稳定性好。研究结果表明,催化剂加氢脱氧性能由SMSI产生的包覆层和氧空位共同决定,Ni的包覆程度与加氢性能呈负相关,而氧空位含量与脱氧性能呈正相关。

Aspects of formation and degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans

The research progress on the mechanisms of formation and degradation of polychlorinated dibenzo-p-dioxins ( PCDDs ) and dibenzofurans ( PCDFs ) is reviewed. The primary sources of PCDD/Fs are chemical, thermal, photochemical and enzymatic reactions. Most of the thermal sources result in emissions into air. The studies on the photodegradation and biodegradation offer promise for destruction of PCDD/Fs in environment.

A novel molecular distance edge vector as applied to chemical modeling of quantitative structure-retention relationships:Various gas chromatographic retention behaviors of polychlorinated dibenzofurans on different polarity-varying stationary phases

Based on the identical group as a pseudo atom instead of a typical atom, a novel modified molecular dis-tance-edge (MDE) vector μ was developed in our laboratory to characterize chemical structure of polychlorinated diben-zofurans (PCDFs) congeners and/or isomers. Quantitative structure-retention relationships (QSRRs) between the new VMDE parameters and gas chromatographic (GC) retention behavior of PCDFs were then generated by multiple linear regression (MLR) method for non-polar, moderately polar, and polar stationary phases. Four excellent models with high correlation coefficients, R=0.984-0.995, were proposed for non-polar columns (DB-5, SE-54, OV-101). For the moder-ately polar columns (OV-1701), the correlation coefficient of the developed good model is only 0.958. For the polar col-umns (SP-2300), the QSRR model is poor with R=0.884. Then cross validation with leave-one out of procedure (CV) is performed in high correlation with the non-polar (Rcv=992-0.974) and weakly polar (Rcv=921) columns and in little cor-relation (Rcv=0.834) with the polar columns. These results show that the new μ vector is suitable for describing the re-tention behaviors of PCDFs on non-polar and moderately polar stationary phases and not for the various gas chroma-tographic retention behaviors of PCDFs on the different po-larity-varying stationary phases.